Plural coated article and process for making same

ABSTRACT

A radiation polymerizable protective coating composition or paint, coated articles bearing such a protective radiation polymerizable paint, which on a non-polymerizable solvent, pigment, initiator and particulate filler-free basis consists essentially of a binder solution of: (1) between about 90 and about 10 parts of a thermoplastic vinyl polymer free of olefinic unsaturation and prepared from at least about 85 weight percent of monofunctional vinyl monomers: (2) between about 10 and about 90 parts of vinyl solvent monomers for said vinyl polymer, at least about 10 weight percent, preferably at least about 30 weight percent, of said solvent monomers being selected from the group consisting of divinyl monomers, trivinyl monomers, tetravinyl monomers and mixtures thereof; and (3) between about 0.05 and about 1.0 parts per 100 parts of the total of said thermoplastic vinyl polymer and said vinyl solvent monomers of a mono- or diester of phosphoric acid bearing one or more sites of vinyl unsaturation. The composition exhibits excellent quality and good adhesion to a variety of substrates, in particular metals, including vapor deposited metals. Preferred articles bearing such a coating are prepared by: applying a base coat to a substrate and curing the same; vapor depositing a coating of a metal over the surface of the base coat; and applying to and curing on the surface of the base coat; and applying to and curing on the surface of the deposited metal the radiation polymerizable topcoat, preferably with little or no pigment contained therein.

This application is a divisional of prior application Ser. No. 500,832,filed Aug. 26, 1974 and now U.S. Pat. No. 3,987,127, which, in turn, isa Continuation-in-Part of Ser. Nos. 431,632 and 431,654 both filed Jan.8, 1974 and now abandoned.

The invention described herin relates to coated articles bearing aradiation polymerizable coating of excellent quality which displaysunusually good adhesion to a variety of substrates and to processes forpreparing such articles.

More particularly, this application relates to radiation polymerizablecoating compositions which are particularly suited as corrosion andabrasion resistant protective coatings for vapor deposited metalsurfaces as well as to articles comprising such a vapor deposited metalsurface bearing the protective coating and processes for preparing thesame. Such protectively coated, vapor deposited metal bearing articlesare a particularly preferred embodiment of the invention since they aresuitable for use as a substitute for plated metal surfaces used for trimor brightwork on the exterior of automobiles.

The radiation polymerizable coating compositions disclosed inconcurrently filed application entitled "Protective Coating Composition,Plural Coated Article and Process for Making Same -- A", which is acontinuation-in-part of both Ser. No. 393,702, filed Aug. 31, 1973 andSer. No 431,633 filed Jan. 8, 1974 and now both abandoned, form coatingsof excellent quality which display unusually good abrasion resistance.While the outstanding properties of those compositions effectively solvemany of the problems associated with providing protective coatings for avariety of substrates, and in particular for substrates bearing vapordeposited metals they do not provide adequate corrosion and waterresistance to allow exterior automotive use of vapor metallizedmaterials.

The coating compositions of this invention solve such problems byproviding improved corrosion and water resistance.

BRIEF DESCRIPTION OF THE INVENTION

The coating compositions of this invention, on a non-polymerizablesolvent, pigment, initiator and particulate filler-free basis consistessentially of a binder solution of: (1) between about 90 and about 10parts of a saturated, thermoplastic vinyl polymer prepared from at leastabout 85 weight percent of monofunctional vinyl monomers; (2) betweenabout 10 and about 90 parts of vinyl solvent monomers for said vinylpolymer, at least about 10 weight percent, preferably at least about 30weight percent, of said solvent monomers being selected from the groupconsisting of divinyl monomers, trivinyl monomers, tetravinyl monomersand mixtures thereof; and (3) between about 0.05 and about 1.0 parts per100 parts of the total of said thermoplastic, vinyl polymer and saidvinyl solvent monomers of a mono- or diester of phosphoric acid bearingone or more sites of vinyl unsaturation and having the formula: ##STR1##where: R = H, Cl or CH₃

A = c_(n) H_(2n), 2 ≦ n ≦ 6

R'=h, c₁ to C₄ alkyl or C₁ to C₄ chloro- or bromo-alkyl

These coating compositions, which are radiation polymerizable, arepreferably cured by exposure to ionizing radiation or ultravioletradiation. The coating compositions provide an excellent protectivesurface which adheres well to a variety of substrates, in particularmetals and vapor deposited metals, and, thus, can be employed in thepreparation of a wide variety of articles. One such preferred article ormaterial, which is useful as a substitute for metal plated materialsused for trim or brightwork on the exterior of automobiles, is preparedby: (1) vapor depositing a metal layer on the surface of a preparedsubstrate; (2) coating the deposited metal surface with the radiationpolymerizable coating of this invention; and (3) curing the coating byexposure to radiation, preferably ionizing radiation or ultravioletradiation.

The radiation polymerizable coating composition and the coated articlesformed therefrom as well as the processes for preparing the same will bedescribed more fully in the detailed description of the invention whichfollows.

PRIOR ART

An article entitled "Radiation Curing of Mixture of DiallylphthalatePrepolymer and Vinyl Monomer" by Gatoda et al appearing at NipponGenshiryoku Kenkyusho Nempo 1970, JAERL/5026, 121-9 (Japan) disclosesradiation polymerizable coating compositions which may contain severalof the organophosphate esters within the purview of this invention. Thearticle further teaches the strong adhesion of the diallylphthalateprepolymer-vinyl monomer-organophosphate ester coatings to metalsurfaces as a shop primer to prevent corrosion. However, the articleteaches the use of the organophosphate esters only in amounts equal toor greater than 2 weight percent based on the total of the other twocomponents. In this connection the article also teaches that as theamount of organophosphate ester is increased the salt water resistanceof the coating is increased. These teachings are contrary to the instantinvention which, as mentioned above, requires between about 0.05 andabout 1.0 parts of organophosphate ester per 100 parts of the total ofthe thermoplastic vinyl polymer and vinyl solvent monomers. In fact, ithas been found quite unexpectedly that while the organophosphate esterswhen included in the coatings of the invention in amounts up to 1% byweight serve to protect the underlying metal from corrosive or chemicalattack, amounts greater than 1% by weight and certainly amounts of 2% byweight or greater cause the coating composition to fail in water.

DETAILED DESCRIPTION OF THE INVENTION I. Radiation Polymerizable CoatingComposition

In this application, the term "paint" is meant to include finely dividedpigment and/or particulate filler as well as other additives in afilm-forming, resin comprising, binder or the binder without pigment,particulate filler, and other additives. Thus, the binder which isultimately converted to a weather and wear-resistant film can be all orvirtually all that is used to form the film, or it can be a vehicle forpigment and other additives.

Prior art radiation polymerizable paints conventionally comprise asolution of an alpha-beta olefinically unsaturated prepolymer in vinylmonomers. Exemplary of such prior art radiation polymerizable coatingsare those disclosed in the following U.S. Pat. Nos. 3,437,512;3,437,513; 3,437,514; 3,528,844; 3,542,586; 3,582,587; 3,560,245;3,577,262; 3,577,263; 3,577,264; 3,577,265; 3,585,526; 3,586,527;3,586,528; 3,586,529; 3,586,530; 3,586,531; 3,591,626; 3,595,687;3,632,399; 3,632,400; 3,641,210; 3,642,939; 3,649,337; 3,650,811;3,650,812; 3,650,813; 3,660,143; 3,660,144; 3,660,145; 3,660,371; and3,679,447. In these patents, the alpha-beta olefinically unsaturatedprepolymer is defined as having olefinic unsaturation provided by analpha-beta olefinically unsaturated monomer; or more particularly, as aresin having pendant unsaturation or olefinic unsaturation between thetwo terminal carbons of a polymer side chain. It is this pendantunsaturation which permits the prepolymer to not only polymerize withvinyl solvent monomers, but also to crosslink and thus form a toughsolvent and weather-resistant coating. Other paints which are radiationpolymerizable at low radiation dosages and which comprisemonounsaturated monomers and a saturated prepolymer containing fromabout 25 to about 65 mole percent of certain hydroxy acrylates have beendisclosed in U.S. patent application Ser. No. 295,649, filed Oct. 6,1972 and now abandoned. Still other paints which are radiationpolymerizable and which comprise conventional alpha-beta olefinicallyunsaturated prepolymers and vinyl monomers in combination with betweenabout 5 and about 25 weight percent based on the total formula weight ofthe paint of a saturated, thermoplastic vinyl resin are disclosed inU.S. patent application Ser. No. 375,992 filed July 2, 1973 now U.S.Pat. No. 3,895,171.

While each of the discussed prior art coatings exhibits a variety ofexcellent properties, each suffers from certain disadvantages. Polymersbearing polymerizable unsaturation, i.e., alpha-beta olefinicunsaturation, are generally prepared by at least a two-stage synthesiswhich is time consuming and expensive. Polymers bearing hydroxylfunctionality can be prepared by a single stage synthesis, but at thehydroxyl levels required for effective crosslinking (25 to 65 molepercent), the water resistance of the final cured film is significantlyimpaired.

The radiation polymerizable coating compositions of this invention,which overcome the deficiencies of prior art coatings, on anon-polymerizable solvent, pigment, initiator and particulatefiller-free basis, consist essentially of: (1) between about 90 andabout 10 parts of a saturated, thermoplastic vinyl polymer prepared fromat least about 85 weight percent of monofunctional vinyl monomers; (2)between about 10 and about 90 parts of vinyl solvent monomers for saidvinyl polymer, at least about 10 weight percent, preferably at leastabout 30 weight percent, of said solvent monomers being selected fromthe group consisting of divinyl monomers, trivinyl monomers, tetravinylmonomers and mixtures thereof; and (3) between about 0.05 and about 1.0parts per 100 parts of the total of said thermoplastic, vinyl polymerand said vinyl solvent monomers of a mono- or diester of phosphoric acidbearing one or more sites of vinyl unsaturation and having the formula:##STR2## where R = H, Cl or CH₃

A = c_(n) H_(2n), 2 ≦ n ≦ 6

R' = h, c₁ to C₄ alkyl or C₁ to C₄ chloroalkyl or bromoalkyl

A. Saturated, Thermoplastic, Vinyl Resin Polymer

The saturated, thermoplastic, vinyl resin polymers useful in the paintcompositions of this invention may be prepared from a single vinylmonomer or from mixtures of vinyl monomers by conventionalpolymerization techniques, e.g., suspension, emulsion, bulk or solutionpolymerization using conventional free radical initiators such asperoxides and hydroperoxides as well as azobis(isobutyronitrile). Theterm "vinyl monomer" as used herein refers to a monomeric compoundhaving a ##STR3## terminal group and excludes allylic compounds.Preferred monomers for preparation of the vinyl homopolymer or copolymerresins are monofunctional monoacrylates and monomethacrylates as well asmonovinyl hydrocarbons. The most preferred monomers are esters ofacrylic or methacrylic acid and C₁ -C₈ monohydric alcohols, e.g., methylmethacrylate, butyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate,cyclohexyl acrylate and mixtures thereof. Monovinyl hydrocarbonssuitable for use in forming polymers are styrene and substitutedstyrenes, such as alpha-methyl styrene, vinyl toluene, t-butyl styrene,chlorostyrene and mixtures thereof.

As indicated above, the saturated thermoplastic vinyl resin polymers orcopolymers useful in paints of this invention should be formed from atleast 85 weight percent of monofunctional vinyl monomers. However,difunctional monovinyl monomers such as acrylic and methacrylic acids,acrylamide, methacrylamide, 2-hydroxyethyl methacrylate,methacryloyloxyethyl phosphate and 2-acrylamido2-methylpropanesulfonicacid, may be used as minor component of the polymer, i.e., up to acombined total of about 15 weight percent. The incorporation of suchmonomers may be desirable in some cases to provide a measure of polarityto the coating resin. However, it should be recognized that aconcomitant effect of increased polarity is increased water sensitivity.Thus, it is preferred not to employ such polar monomers in thepreparation of the paints of this invention unless necessary for theparticular application.

The essentially linear, gel-free thermoplastic polymers formed from thepreferred monomers set forth above should have number average molecularweights (M_(n)) of less than about 250,000 but not less than about2,000. Preferred values lie between about 3,000 and about 100,000 withmost preferred values being between about 5,000 and about 50,000.

While the paint composition of the invention may include mixtures ofpolymers or copolymers formed from vinyl monomers as discussed above, itis preferred that the paint solution contain little or no alpha-betaolefinically unsaturated resins as conventionally employed inradiationcurable paint resins discussed above. The term "alpha-betaolefinically unsaturated resin" as used in this context is intended tomean an organic resin having olefinic unsaturation provided by analpha-beta olefinically unsaturated monomer. More specifically the termis intended to mean olefinic unsaturation between the two terminalcarbons of a polymer side chain. Even though the properties of thepaint, particularly adhesion properties, will be affected by itsinclusion, up to 5 weight percent based on the total of polymer andsolvent monomer of such alpha-beta olefinically unsaturated resins maybe tolerated.

B. Vinyl Solvent Monomers

At least about 10 weight percent and preferably at least about 30 weightpercent of the vinyl solution monomers of the paint compositions of thisinvention are selected from the group consisting of divinyl monomers,trivinyl monomers, tetravinyl monomers and mixtures thereof. These di-,tri-, and tetravinyl compounds are preferably acrylates, methacrylatesor vinyl hydrocarbons. The most preferred are esters of acrylic ormethacrylic acids and polyhydric C₂ -C₈ alcohols, e.g., neopentylglycoldimethacrylate, 1,6-hexanediol diacrylate, 1,3-butylene dimethacrylate,tri-methylolpropane triacrylate, pentaerythritol triacrylate,pentaerythritol tetraacrylate, etc. Other divinyl monomers which may beemployed are disclosed in U.S. Pat. Nos. 3,586,528; 3,586,529;3,586,530; 3,586,531; and 3,595,687. These divinyl compounds are formedby reacting either a monepoxide or diepoxide with acrylic acid ormethacrylic acid and subsequently reacting the resultant estercondensation product with a saturated acyl halide. Further tetravinylcompounds which may be employed are disclosed in U.S. Pat. Nos.3,586,526; 3,586,527; and 3,591,626. These tetravinyl compounds areformed by reacting a diepoxide with acrylic acid and/or methacrylic acidand then subsequently reacting the resultant ester condensation productwith a vinyl unsaturated acyl halide.

The remainder of the vinyl solvent monomers used in combination with thesaturated, thermoplastic vinyl resin polymers or copolymers discussedabove may be monofunctional, monovinyl monomers such as those used inthe preparation of the polymer or copolymer.

C. Mono- or Diesters of Phosphoric Acid

The coating compositions of the invention include between about 0.05 andabout 1.0 parts, preferably between about .1 and about .6 parts, andmore preferably between about .2 and about .5 parts, per 100 parts ofthe total of said saturated, thermoplastic, vinyl resin polymer and saidvinyl solvent monomers of a mono- or diester of phosphoric acid bearingone or more sites of vinyl unsaturation and having the formula: ##STR4##where: R = H₁ Cl or CH₃

A = c_(n) H_(2n), 2 ≦ n ≦ 6

R'=h₁ c₁ to C₄ alkyl or C₁ to C₄ chloro- or bromo-alkyl

Representative of the various species of organophosphate esters fallingwithin the above formula are: (1) 2-methacryloyloxyethyl phosphate(R=CH₃, A=--CH₂ CH₂ --, R'=H, m=1); (2) di(2-methacryloyloxyethyl)phosphate (R=CH₃, A=--CH₂ CH₂ --, m=2); (3) 2-acryloyloxyethylphosphate(R=H, A=--CH₂ CH₂ --, R'=H, m=1); (4) di-(2-acryloyloxyethyl)phosphate(R=H, A=--CH₂ CH₂ --, m=2); (5) methyl 2-methacryloyloxyethyl phosphate(R=CH₃, A=CH₂ CH₂ --, R'=CH₃, m=1); (6) ethyl methacryloyloxyethylphosphate (R=CH₃, A=--CH₂ CH₂ --, R'=CH₃ CH₂ --, m=1); (7) methylacryloyloxyethyl phosphate (R=H, A=--CH₂ CH₂ --, R'=CH₃, m=1); and (8)ethyl acryloyloxyethyl phosphate (R=H, A.tbd. CH₂ CH--₂, R'=CH₃ CH₂ --,m=1).

The preferred organophosphate esters are 2-methacryloyloxyethylphosphate, di(2-methacryloyloxyethyl) phosphate, 2-acryloyloxyethylphosphate and di(2-acryloyloxyethyl) phosphate, with 2methacryloyloxyethyl phosphate being most preferred. Exemplary of themany other organophosphate esters which are encompassed by the aboveformula are those in which the R' groups of (1) through (8) are replacedby propyl butyl and isobutyl groups or by chloro or bromo substitutedethyl, propyl, butyl and isobutyl groups.

D. Photoinitiators

When the paint compositions of this invention are polymerized byexposure to ultraviolet radiation it may be desirable to include aphotoinitiator or photosensitizer in the paint. The use of suchphotoinitiators and examples of various ones which may be employed willbe discusses hereinafter in greater detail.

E. Inert Solvents and Other Additives

Inert solvents, i.e., solvents that do not enter into the polymerizationor crosslinking reactions of the paint binder polymer/monomer systemunder normal exposure to radiation, can be added to the coatingformulation to reduce viscosity and aid in control of applicationproperties. Such solvents are normally selected to be substantially morevolatile than the monomeric constituents of the paint formulation, thusallowing them to evaporate prior to irradiation of the coatings.Suitable solvents include, by way of example and not by way oflimitation: toluene; butyl acetate; methylethyl ketone; isopropanol;benzene; tetrahydrofuran, dioxane, methylisobutyl ketone; methylenechloride; chloroform; ethylene chloride; trichloroethylene;trichloroethane; and mixtures thereof. Additional materials such ascatalysts, pigments, plasticizers, etc., all of which are well known inthe formulation of coating compositions and, in particular in the art ofradiation polymerizable coating compositions, may be included in thecoating compositions of the invention.

II. Coated Articles and Processes for Making Same

The radiation polymerizable points discussed above display unusuallygood adhesion to a variety of substrates including wood, paper, glass,shaped polymeric surfaces and metal, particularly vapor deposited metalsurfaces. In addition to these outstanding adhesion properties, thecoatings of the invention also exhibit excellent water resistance andintercoat adhesion. The novel paint compositions of the invention, likeprior art radiation polymerizable paints discussed above, may be appliedto a variety of substrates by conventional means, e.g., brushing,spraying, roller coating, flow coating, etc., to an average thicknesswhich is preferably in the range of from about 0.1 to about 4.0 milsdepending on the substrate and the intended end use of the coatedproduct.

The novel paint compositions of the invention may be cured orpolymerized by exposure to radiation, preferably ionizing radiation orultraviolet light. In either case, the paint compositions may be curedat relatively low temperatues, e.g., between room temperature (20° to25° C) and the temperature at which significant vaporization of its mostvolatile component is initiated, (ordinarily between about 20° C andabout 70° C).

The term "ionizing radiation" as employed herein means radiation havingsufficient energy to remove an electron from a gas atom, forming an ionpair, and hence radiation with energy of, or equivalent to, about 5,000electron volts. The preferred method of curing paint films of thisinvention by exposure to ionizing radiation is by subjecting such filmsto a beam of polymerization-effecting electrons which is at its sourceof emission within the range of, or equivalent to, 150,000 to 450,000electron volts. In this method of curing, it is preferred to employ aminimum of 25,000 electron volts per inch of distance between theradiation emitter and the workpiece where the intervening space isoccupied by air. Adjustment is made for the resistance of theintervening gas which is preferably an oxygen-free inert gas such asnitrogen, helium, or combustion products of natural gas. It is, however,within the scope of the use of ionizing radiation to effectpolymerization using either that which is conventionally termed "highenergy particle radiation" or "ionizing electromagnetic radiation".

When such ionizing radiation is employed to cure the paint compositionsof this invention, the radiation energy is applied at dose rates of fromabout 0.1 to about 100 Mrads per second upon a preferably movingworkpiece with the coating receiving a total dose in the range of fromabout 0.1 to about 100, preferably from about 1 to about 25 Mrads. Theabbreviation "Mrads" as employed herein means 1 million Rads. The term"Rads" means that dose of radiation which results in the absorption of100 ergs of energy per gram of absorber, e.g., coating film. Theelectron emitting means may be a linear electron accelerator capable ofproducing a direct current potentially in the range hereinbefore setforth. In such a device, electrons are ordinarily emitted from a hotfilament and accelerated through a uniform voltage gradient. Theelectron beam, which may be about 1/8 inch in diameter at this point isscanned in one direction to make a fan-shaped beam and then passedthrough a metal window, e.g., a magnesium-thorium alloy of about 0.003inch thickness.

As mentioned above, the radiation polymerizable coating compositions ofthis invention may also be cured by exposure to ultraviolet light.Preferably, paint compositions according to this invention which arecured by exposure to ultraviolet light contain little or no pigment.Upon exposure to light of wave lengths less than about 390 mμ, most ofthe vinyl monomers employed in the paint compositions of this inventionwill fragment and produce radicals which can initiate polymerization.However, in order to make more efficient use of the output of highintensity UV sources and thereby attain a commercially feasible rate ofcure, it is preferred to include a photoinitiator or photosensitizer incompositions to be cured by ultraviolet radiation.

Photoinitiators (or sensitizers) are substances, generally organiccompounds which, upon exposure to light of appropriate wave length, giverise to or promote the production of polymerization initiating species.It is preferred to employ a photoinitiator which decomposes to yield, orotherwise results in the production of, one or more free radical speciesupon exposure to light having a wavelength of less than about 380 mμ. Inorder for any photochemical reaction to occur, there must be someoverlap between the wavelength of light incident upon the reactionmedium (the coating) and the wave length absorbed by the photoinitiatingspecies. Thus, the selection of an appropriate photoinitiator dependsnot only upon its efficacy as a polymerization initiator, but also uponthe light source(s) used.

Many different types of free-radical initiators and sensitizers havebeen studied in acrylic systems and these are well known in the art. Therate of cure of the paint compositions of this invention, is, of course,a function of the type of initiator and its concentration, the intensityof incident light of appropriate wavelength and the type andconcentration of polymerization inhibitors. Also, the detailedcompositions of the coating formulation can have a significant effect onthe rate of cure, especially at low exposure levels. Thus, in the endanalysis, the amount of ultraviolet radiation which is necessary toachieve the desired properties in the final film formed from the paintcompositions of this invention will vary with the composition of thepaint itself and one of ordinary skill in this art will be able todetermine the optimal exposure to UV light in view of the variousfactors discussed above with a minimum of experimentation.

Included among the many suitable photoinitiators are: organic carbonylcompounds such as acetone, benzophenone, benzathrone, benzoin, benzoinmethyl ether, 2,2-diethoxy-acetophenone,2,2-dimethoxy-2-phenylacetophenone, benzoin n-butyl ether and benzoiniso-butyl ether; peroxides such as hydrogen peroxide, di-t-butylperoxide, ergosterol peroxide and benzoyl peroxide; organic sulphurcompounds such as diphenyl disulfides, dibenzoyl disulfides anddibenzothiazol disulfides; and azo compounds such as2,2'azobis-(2-methylpropionitrile), α,α'-azobisisobutyronitrile,azomethane, azothane, α-azobis-1-cyclohexane carbonitrile; and otherwell known initiators such as 2-ethylhexyl-2-cyano-3,3-diphenylacrylate.Based on availability, solubility in the coating compositions of thisinvention, freedom from color and efficiency of curing at minimal UVexposure levels, the preferred photoinitiators are2,2-diethoxyacetophenone, benzophenone and 2-ethylhexyl-2-cyano-3,3-diphenylacrylate. The amount of each photoinitiator necessary tosuitably initiate polymerization in the paint compositions of thisinvention when curing by exposure to UV light will be apparent to thoseskilled in the art. It has been found, however, that generally thepresence of a photoinitiator in the amount of from about 0.5 to about5.0 parts per 100 parts of the total reactive vehicle solids in thepaint composition will produce adequate curing upon exposure to a lowpressure ultraviolet lamp.

A. Coated Articles Including Vapor Deposited Metals

As discussed above, the coating compositions of this invention areparticularly suited as abrasion and corrosion resistant protectivecoatings for surfaces bearing vapor deposited metals. Such coatedarticles bearing vapor deposited metals are a particularly preferredembodiment of this invention since they are suitable for use as asubstitute for plated metal surfaces used for trim or brightwork on theexterior of automobiles.

Vapor deposition of metals, and in particular vacuum metallizing, is asimple and relatively low cost process by which thin layers of metalsare deposited on prepared surfaces of substrates such as metal, plastic,glass, paper and other materials. Surfaces bearing vapor depositedmetals, and in particular plastic substrates bearing thin deposits ofaluminum, have been considered as a substitute for plated metal surfacesused for trim or brightwork on the exterior of automobiles. Since vapordeposition of metals produces very attractive surfaces and issubstantially less expensive than processes for metal plating, such aschrome plating, it would appear to be ideally suited for producing suchtrim or brightwork. However, due to severe abrasion and corrosionproblems, articles produced by vapor depositing metals have not beendeemed suitable for exterior automotive use. The coating compositions ofthis invention, when applied over the surface of such vapor depositedmetals afford the protection necessary to overcome this problem.

Vapor deposition of metals is well known and the detailed procedureswill be apparent to those skilled in the art. Physical vapor deposition,the process most commonly used for decoration of plastics, involvesformation of the coating by physical means alone. Two of the mostcommonly used techniques, i.e., resistive heating and electron beamheating, involve stepwise heating in vacuum, first melting and thenvaporizing the material to be deposited. Other well known techniquessuch as sputtering may also be employed. The choice of methods dependsto some extent on the material to be deposited. A review of physicalvapor deposition techniques may be found in Vapor Deposition, C. F.Powell, J. H. Oxley and J. M. Blocker, Jr., eds., John Wiley & Sons,Inc. New York (1966), p. 221 ff. Resistive heating of a tungstenfilament or basket or of a refractory crucible is commonly used forvapor deposition of aluminum, the most common evaporant for depositionon plastic parts. Electron beam heating of an evaporant contained in asuitable crucible or hearth is recommended for deposition of alloys andmetals which have low vapor pressures or which form alloys withconventional filaments or crucibles at normal evaporating temperatures.Iron-chrome alloys can be deposited best using electron-beam heatingtechniques or sputtering.

Chemical vapor deposition techniques, also discussed in Powell et al,can in principle also be used in the formation of the composite coatedarticles of this invention. Such techniques involve the transfer ofmaterial across temperature or concentration gradients between thesubstrate and the surrounding atmosphere and formation of coatings bychemical reactions at the surface of the substrate. Chemical vapordeposition techniques often involve heating of the substrate tomoderately high temperatures to form the final metallic coating.Application of these techniques is thus restricted to those substratescapable of withstanding the required process conditions.

B. Preferred Plural Coated Embodiment

The preferred coated article of this invention is prepared by: applyinga base coat to a substrate and curing the coating; vapor depositing ametal layer on the base coat; applying the coating composition of thisinvention over the metallized surface; and curing the coating withradiation.

C. Base Coat Compositions

The base coat fills minor surface imperfections of the substrate,provides a high-gloss surface to receive the metal deposit, improvesadhesion of the deposit, and reduces the quantity of gas liberated fromthe substrate at reduced pressures. In selecting a base coat it is thusimportant that the composition display good intercoat adhesion, i.e.,adhere well to both the substrate and the metal layer.

The lacquers and the radiation polymerizable compositions useful as basecoats in the process of this invention may be applied by conventionalmeans, e.g., spray coating, dip coating, flow coating, etc., to anaverage thickness which is preferably in the range of from about 0.1 toabout 4.0 mils. The lacquers useful as base coats are well-known in theprior art and may be air dried or heat cured. Most bake-curing lacquerscure in 1-3 hours at temperatures ranging from 140° to 180° C. Theradiation polymerizable base coats may be cured at relatively lowtemperatures, e.g., between room temperature (20° to 25° C). and thetemperature at which significant vaporization of its most volatilereactive component is initiated, (ordinarily between about 20° C. andabout 70° C). The radiation energy is applied at dose rates of fromabout 0.1 to about 100 Mrads per second upon a preferably movingworkpiece with the coating receiving a total dose in the range of fromabout 0.1 to about 100, preferably from about one to about 25 Mrads. Itwill be appreciated that the use of radiation polymerizable base coatswill substantially lessen the processing time necessary for producingthe plural coated articles of the invention.

The lacquer base coats which may be employed are well-known in the artof vapor deposition, and in particular vacuum metallizing, and consistessentially of a crosslinkable or curable resin in a volatile solvent.Representative of the organic resins which may be employed individuallyor in combination to formulate such a lacquer are: acrylic resins, alkydresins (pure and modified), polyesters, conventional varnishes,urea-formaldehyde resins, vinyl polymers, acrylonitrile polymers,phenolic resins, cellulosic resins, polyurethanes, butyl rubber andchlorinated butyl rubber, silicone resins, melamine-formaldehyde resins,polyestyrenes, natural rubber, and modified phenolic resins. Numerousbase coats employing such organic resins commercially available.

Radiation polymerizable base coat compositions which may be employed inthe process and articles of this invention include the compositionemployed as the radiation polymerizable top coat, i.e., the coatingcomposition of this invention described above in detail. Also, the basecoat may be the composition disclosed and claimed in theabove-identified application entitled "Protective Coating Composition,Plural Coated Article and Process for Making Same-A". That compositioncorresponds to the composition of this invention with the exception thatit does not include the mono- or diester of phosphoric acid.

A still further preferred base coat for the preferred plural coatedarticles of this invention is the same as the top coat of this inventionwith the exception that the mono- or diester of phosphoric acid isreplaced by a triester in amounts ranging from about 1 to about 15,preferably about 3 to about 10, parts per 100 parts of the total of thethermoplastic vinyl polymer and the vinyl solvent monomers. Thistriester additive has the formula: ##STR5## where: R = H, Cl or CH₃

A = c_(n) H_(2n), 2 ≦ n ≦ 6

R' = c₁ to C₄ alkyl; C₁ to C₄ bromo- or chloroalkyl; or

Finally, the radiation polymerizable base coat may comprise afilm-forming solution which, exclusive of non-polymerizable solvents,pigments and other non-reactive components consists essentially of: (1)between abpout 90 and about 10 parts, preferably between about 70 andabout 30 parts, of an alpha-beta olefinically unsaturated urethanemodified organic resin; and (2) between about 10 and about 90,preferably between about 30 and about 70, parts of vinyl solventmonomers, i.e., vinyl monomers which act as solvents for the alpha-betaolefinically unsaturated urethane-modified organic resin. Such afilm-forming radiation polymerizable composition is disclosed in U.S.Pat. No. 3,437,514, the entire disclosure of which is incorporatedherein by reference.

The alpha-beta olefinically unsaturated urethane-modified organic resinhas a molecular weight greater than 1000, preferably between 5000 and50,000 and still more preferably between 5000 and 20,000 and containsbetween about 0.5 and about 5, preferably between about 0.5 and about 3,units of olefinic unsaturation per 1000 units of molecular weight. Theresin is formed by reacting a diisocyanate monomer and an organic resinhaving in its molecular structure a plurality of hydrogen atoms whichare labile with respect to the isocyanate group, e.g., a labile hydrogenatom of an amine, amide, alcohol or carboxylic acid, and subsequentlyreacting the product with a hydroxylated vinyl monomer. The organicresin used in the preparation may be a polyester or a resin formed bycopolymerization of acrylic monomers, i.e., acrylic and methacrylicacids as well as esters formed therefrom. Exemplary of the manydiisocyanates which may be employed to form the alpha-beta definicallyunsaturated resins are: 2,4 tolylene diisocyanate, 65/35 tolylenediisocyanate, 80/20 tolylene diisocyanate, 4,4' Diphenylmethanediisocyanate, dianisidine diisocyanate, tolidene diisocyanate,hexamethylene diisocyanate, etc.

The formulation of various polyesters, such as hydroxy terminatedpolyesters, and polymers or copolymers formed from acrylic monomers andbearing functional groups which will react with the diisocyanatecompounds are well-known in the art. Exemplary of the many monomerswhich may be employed in the vinyl monomers compound constituent of theurethane-modified base coat are: esters of C₁ -C₈ monohydric alcoholsand acrylic or methacrylic acids, e.g., methyl methacrylate, ethylacrylate, butyl acrylate, butyl methacrylate, octyl acrylate,2-ethylhexyl acrylate, etc.; esters of alcohols of higher carbonnumbers, e.g., C₉ -C₁₅ as well as difunctional alcohols and acrylic ormethacrylic acids; vinyl hydrocarbon monomers, e.g., styrene andalkylated styrenes such as vinyl toluene, alpha-methylstyrene, etc.;divinyl and tetravinyl compounds; and small amounts of other vinylmonomers such as acrylonitrile, acrylamide or vinyl acetate.

The urethane-modified organic resin base coats may also includeadditives such as pigments, catalysts, inert solvents, etc. as discussedabove with respect to top coats.

It should be appreciated that various coating formulations are withinthe scope of this invention and that such compositions may be applied tovarious substrates in the manner described. Therefore, it should beunderstood that the following specific examples are presented by way ofillustration and not by way of limitation.

EXAMPLE I

A radiation polymerizable coating is prepared from the followingmaterials in the manner hereinafter set forth:

                  Step 1                                                          ______________________________________                                        Preparation of Paint Binder Resin                                                                  Parts by Weight                                          ______________________________________                                        (1) Water              150                                                    (2) Triton X200*       5.2                                                    (3) 1% aquous K.sub.2 S.sub.2 O.sub.8                                                                30                                                     (4) Methyl methacrylate                                                                              300                                                    (5) Water              270                                                    (6) Triton X200*       3.5                                                    (7) Triton X305**      10.7                                                   (8) K.sub.2 S.sub.2 O.sub.8                                                                          1.2                                                    (9)Octanethiol         2.1                                                    ______________________________________                                         *Triton X200, a product of Rohm & Haas Co., is an anionic surfactant          containing 28% active component (the sodium salt of an alkyl aryl             polyester sulfonate).                                                         **Triton X305, a product of Rohm & Haas Co., is a nonionic surfactant         containing 70% active component (an alkylarylpolyether alcohol averaging      30 ethylene oxide units).                                                

Items 1 and 2 are charged to a reactor provided with a condenser, athermometer, an agitator, and a dropping funnel. The mixture is boiledto remove dissolved oxygen, and cooled slightly to 90° C. Item 3 isadded. A mixture of the remaining ingredients is then added slowly overa period of about 40 minutes while maintaining the reaction mixture atreflux. Following the monomer addition, the mixture is maintained atreflux for an additional 2 hours.

The latex so obtained is cooled and coagulated by additing it dropwiseto three volumes of rapidly stirred methanol heated to about 40° C. Thepolymeric precipitant is isolated by filtration, washed with methanol,dried in vacuo and used in the subsequent preparation of coatingmaterials. The polymer molecular weight is about 10,000.

                  Step 2                                                          ______________________________________                                        Formulation of Coating                                                                             Parts by Weight                                          ______________________________________                                        (1) Polymer from Step 1                                                                              24.2                                                   (2) Neopentylglycol diacrylate                                                                       36.4                                                   (3) 2-ethylhexyl acrylate                                                                            39.4                                                   (4) 2-methacryloyloxyethyl phosphate                                                                 .5                                                     (5) Butyl acetate      40                                                     (6) Toluene            40                                                     (7) Methyl ethyl ketone                                                                              10                                                     (8) Isopropanol        10                                                     ______________________________________                                    

A solution of polymer is prepared using the above listed monomers andsolvents. The film-forming solution so obtained is applied to a plasticsubstrate bearing a vacuum deposited aluminum surface and cured thereonunder an inert atmosphere by electron beam irradiation using a totaldosage of 9 Mrads (voltage 275 KV, current 40 ma.).

The coating so obtained displays no softening or color change, and theunderlying metal is similarly unaffected by 240 hours exposure to waterat 90° F. No failure is observed in 168 hours 5% salt spray exposure. Byway of comparison, a similarly prepared coating from which the phosphateadditive is omitted, when subjected to similar test conditions, isobserved to allow attack on and virtually complete removal of theunderlying metal adjacent to a scribed line.

EXAMPLE II

A coating composition is prepared in accordance with the procedures ofExample I with the exception that: (1) one part of octanethiol is usedin the preparation of the polymer which has a molecular weight (M_(n))of about 17,000; (2) 0.3 parts of di(2-methacryloyloxyethyl) phosphateare employed as the organophosphate ester component; and (3) 3 parts per100 parts of reactive solids in the coating composition of 2,2diethoxyacetophenone are added. This coating composition is applied to asubstrate comprising a surface of vapor deposited aluminum and cured byexposure to UV light. The coating exhibits excellent abrasion and waterresistance.

EXAMPLE III

The procedures of Example I are repeated with the exception that: (1)4.5 pats of octanethiol are used in the preparation of the polymer whichhas a molecular weight (M_(n)) of about 5,000; and (2) .1 parts of2-acryloyloxyethyl phosphate are employed as the organophosphate estercomponent. The coating composition, when applied to and cured in situ ona plastic substrate bearing a vapor deposited antimony surface, forms anabrasion and corrosion resistant surface.

EXAMPLE IV

The procedures of Example I are repeated with the difference that: (1)the polymer is formed from an equimolar mixture of isobutyl methacrylateand methyl methacrylate; (2) the inert solvent portion is comprised ofequal parts by weight butyl acetate and toluene; and (3) 0.7 parts ofdi(2-acryloyloxyethyl) phosphate are employed as the organophosphateester component. The coating composition is sprayed onto two (2)substrates, one having a surface comprising a vapor deposited alloy ofiron and chrome (80% Fe/20% Cr) and the other being a steel panel, andcured by electron beam irradiation. The cured coating adheres well toboth surfaces, and is both abrasion and water resistant.

EXAMPLE V

The procedures of Example I are repeated with the exception that: (1)the polymer is formed from an equimolar mixture of ethyl acrylate,styrene, methyl methacrylate and isobutyl methacrylate; and (2) 0.9parts of methyl 2-methacryloyloxyethyl phosphate are employed as theorganophosphate ester component. The solution is applied to a glasssubstrate bearing a thin film of vacuum deposited aluminum and cured byelectron beam irradiation as in Example I. The surface of the resultantcoated article is both abrasion and corrosion resistant.

EXAMPLE VI

The proedures of Example II are repeated with the exception that: (1)the solution monomers are 1,6 hexanedioldiacrylate and 2-ethylhexylacrylate, present in equal proportions by weight; and (2) 0.95 parts ofethylmethacryloyloxyethyl phosphate are employed as the organophosphatecomponent. The coating composition is applied to metal, glass, wood andplastic substrates and cured by exposure to UV radiation. The curedcoatings are durable and exhibit good adhesion and water resistance.

EXAMPLE VII

The procedures of Example I are repeated with the difference that thefilm forming solution has the following composition:

    ______________________________________                                                             Parts by Weight                                          ______________________________________                                        Polymer (from Step 1)  19.5                                                   Neopentylglycol diacrylate                                                                           43.3                                                   Hydroxyethyl acrylate  37.2                                                   methylacryloyloxyethyl phosphate                                                                     .4                                                     ______________________________________                                    

The solution is adjusted to spray viscosity by dilution with a mixtureof butyl acetate, toluene, methyl ethyl ketone, and isopropanol inproportion by weight 4:4:1:1; sprayed on vapor deposited antimony andcured by exposure to ionizing radiation.

EXAMPLE VIII

The procedures of Example III are repeated with the difference that thefilm-forming solution has the following composition:

    ______________________________________                                                             Parts by Weight                                          ______________________________________                                        (1) Polymer (from Step 1)                                                                            40                                                     (2) Ethyleneglycol dimethacrylate                                                                    40                                                     (3) Hydroxyethyl acrylate                                                                            20                                                     (4) ethylacryloyloxyethyl phosphate                                                                  .8                                                     ______________________________________                                    

The solution is adjusted to spray viscosity by dilution with the inertsolvent mixture described in Example VII and sprayed onto a metal panel.After curing, the composition forms a hard, water resistant and abrasionresistant film.

EXAMPLE IX

A radiation polymerizable coating is prepared from the followingmaterials in the manner hereinafter set forth:

                  Step 1                                                          ______________________________________                                        Preparation of Polymer                                                                             Parts by Weight                                          ______________________________________                                        (1) Methyl methacrylate                                                                              290                                                    (2) Methacrylic acid   10                                                     (3) t-butylperoctoate  1.5                                                    (4) Toluene            300                                                    (5) 10% t-butylperoctoate in toluene                                                                 10                                                     ______________________________________                                    

A mixture of items 1 and 2 is added dropwise over a 2 hour period to areaction flask (equipped with a condenser, thermometer, agitator, anddropping funnel) containing item 3 maintained at reflux. The mixture isrefluxed two to three additional hours; item 4 is charged to the flaskat the end of the first hour. The polymer so obtained has a numberaverage molecular weight of about 13,000.

                  Step 2                                                          ______________________________________                                        Formulation of Coating                                                                             Parts by Weight                                          ______________________________________                                        (1) Polymer from Step 1                                                                              27                                                     (2) Neopentylglycol diacrylate                                                                       35                                                     (3) 2-ethylhexyl acrylate                                                                            38                                                     (4) 2-methacryloyloxyethyl phosphate                                                                 .5                                                     ______________________________________                                    

The polymer solution from Step 1 is mixed with monomers to give theratios of polymer to monomer indicated above. The resulting solution isreduced to spray viscosity (about 15 seconds, Ford cup No. 4) using amixture of butyl acetate, toluene, ethyl acetate and isopropanol inproportion by weight 4:4:1:1.

The film forming composition so obtained is applied to a plasticsubstrate bearing vapor deposited aluminum and cured according to theprocedures of Example I. The coating is essentially unaffected by 240hour exposure to water at 90° F. No failure is observed in 240 hour 5%salt spray.

EXAMPLE X

The procedures of Example IX are followed except that:

(1). a polymer having a molecular weight (M_(n)) of about 7,000 isprepared in accordance with Step 1 using

    ______________________________________                                                             Parts by Weight                                          ______________________________________                                        Methyl methacrylate    200                                                    t-butylperoctoate      3                                                      Toluene                300                                                    7% t-butylperoctoate in toluene                                                                      10                                                     ______________________________________                                    

2.1.0 parts by weight of 2-methacryloyloxyethyl phosphate is admixedwith the polymer and other components to form the coating composition.The composition is applied to and cured in situ on a glass substratecoated with vacuum deposited aluminum to produce a hard, corrosion andabrasion resistant surface.

EXAMPLE XI

The procedures of Example X are repeated with the difference that thecoating formulation comprises: 70 parts by weight polymer; 30 parts byweight neopentylglycol diacrylate; and 2 parts by weight alpha, 2,2diethoxyacetophenone. This formulation is reduced to spray viscosity(about 15 seconds Ford cup No. 4) using a 1:1 mixture of tolyene andbutylacetate.

The film forming composition so obtained is applied to a substrate andcured thereon by exposure for 3 minutes in a nitrogen atmosphere toradiation from a low pressure mercury lamp (intensity about 4 × 10¹⁶photons sec⁻ ¹ cm⁻ ², major UV peak at 2537 angstroms) at a distance of1 inch. The cured coating display adhesion to aluminum and solvent andwater resistance essentially equivalent to those of a comparableelectron beam cured coating.

EXAMPLE XII

The procedure of Example XI is repeated with the difference that thecoating formulation is reduced to spray viscosity, sprayed on a plasticsubstrate coated with vacuum deposited aluminum and cured by exposure toUV light. The cured coating displays excellent water and solventresistance and adhesion to the vacuum deposited metal surface.

EXAMPLE XIII

The procedure of Example X is repeated with the difference that themonomer used in preparation of the polymer comprises 194 parts by weightmethyl methacrylate and 6 parts by weight acrylic acid. The coatingcomposition so formed is reduced to spray viscosity (about 15 secondsFord cup No. 4) using a 1:1 mixture of toluene and butylacetate, andsprayed on both plastic substrated coated with vacuum deposited aluminumand solid aluminum substrates. The coating formulation so applied iscured by exposure for 3 minutes in a nitrogen atmosphere to radiationfrom a low pressure mercury vapor lamp as discussed in Example XI. Thecured coating displays excellent solvent and water resistanceessentially equivalent to those of a comparable electron beam curedcoating.

EXAMPLE XIV

The procedures of Examples XI and XII are repeated with the soledifference that the photoinitiator used is 2-ethylhexyl-2 cyano-3,3diphenylacrylate. Essentially equivalent results are obtained.

EXAMPLE XV

The procedures of Example XIII are repeated with the sole differencethat 3 weight percent of benzophenone is incorporated as thephotoinitiator in lieu of the 2,2 diethoxyacetophenone. Essentiallyequivalent results are obtained. EXAMPLE XVI

Commercially available materials may be used for the polymer. Filmforming solutions are prepared from Acryloid A21LV and Acryloid B48N asset forth hereinafter. Acryloid A21LV is marketed by Rohm & Hass Co. andis described as a methyl methacrylate polymer having Tg=105° C; it issupplied as a 30% by weight solution in a mixture of toluene, methylethyl ketone, and butanol (in proportion by weight 50:40:10) at aBrookfield viscosity of 210-280 cps at 25° C. The number averagemolecular weight is about 13,000. Acryloid B48N is marketed by Rohm &Hass Co. and is described as a methyl methacrylate copolymer havingTg=50° C; it is supplied as a 45% by weight solution in toluene atBrookfield viscosity of 6,000 to 10,000 at 25° C. The number averagemolecular weight is about 15,000. Phosmor M is a product of Yushi SeihinK.K. a subsidiary of Nihon Oil & Fat Co., Ltd. and is primarily2-methacryloyloxyethylphosphate.

Coating compositions A, B, C, D and E are prepared as follows:

    ______________________________________                                                        Parts by Weight                                                               A    B      C      D    E                                     ______________________________________                                        Acryloid B48N (solids basis)                                                                    35     0      0    15   0                                   Acryloid A21LV (solids basis)                                                                   0      23     23   0    65                                  2-ethylhexyl acrylate                                                                           30     40     40   35   5                                   Neopentylglycol diacrylate                                                                      35     37     0    0    0                                   1,6-hexanediol diacrylate                                                                       0      0      37   0    30                                  Trimethylolpropane triacrylate                                                                  0      0      0    50   0                                   Phosmor M         .5     1.4    .7   2.1  .3                                  ______________________________________                                    

All were reduced to spray viscosity using an inert solvent mixture oftoluene, methyl ethyl ketone, butyl acetate and isopropanol. Thesolutions are than sprayed on substrates bearing vacuum depositedaluminum surfaces and cured thereon using an electron beam to give atotal radiation dose of 9 Mrads (voltage 275 KV., current 40 ma). Allthe cured coatings so obtained displayed excellent adhesion to thesubstrates and good solvent and water resistance. Coatings formed fromcompositions A,C and E also display excellent corrosion protection whenimmersed in a 5% aqueous solution of sodium chloride for a period of 30days. The coatings formed from compositions B and D, on the other hand,exhibited poor water resistance. The films formed from D became hazyunder the above test conditions as well as under 240 hours immersion inwater at 90° F.

EXAMPLE XVII

The coatings of Example XVI are compared with a coating from which thethermoplastic polymer is omitted. A mixtue of 50 parts by weight2-ethylhexyl acrylate and 50 parts by weight 1,6-hexanediol diacrylatewas prepared, applied to a substrate and cured under the conditionsspecified in Example XI. The coating obtained displayed very pooradhesion, especially to polymeric substrates.

EXAMPLE XVIII

A plural coated article including a vacuum deposited metal layer isprepared as follows.

A. preparation and Application of Base Coat

    ______________________________________                                                             Parts by Weight                                          ______________________________________                                        (1) Acryloid B82       50                                                     (2) Pentaerythritol triacrylate                                                                      100                                                    ______________________________________                                    

Components (1) and (2) are mixed in the indicated proportions by weight,reduced to spray viscosity (13 sec. Ford Cup No. 4) using an insertsolvent mixture of toluene, methyl ethyl ketone, butyl acetate andisopropanol, applied to an injection molded ABS(acrylonitrile-butadiene-styrene copolymer) plastic substrate, and curedthereon by exposure to an electron beam in an inert atmosphere at 280KV, 40 ma for a total dose of 8 Mrads.

B. application of the Metal Layer

A layer of type 430 stainless steel is deposited on the base coatedsubstrate by a conventional vacuum deposition technique employingelectron beam heating of the evaporant.

C. preparation and Application of Top Coat

    ______________________________________                                                             Parts by Weight                                          ______________________________________                                        (1) Acryloid A21LV     40                                                     (2) neopentylglycol diacrylate                                                                       30                                                     (3) 2-ethyl hexyl acrylate                                                                           30                                                     (4) 2- methacryloyloxyethyl phosphate                                                                0.5                                                    ______________________________________                                    

The listed components are mixed in the indicated proportions by weight,reduced to spray viscosity with an inert solvent mixture of toluene andmethyl ethyl ketone, applied to the metallized substrate, and cured byexposure to an electron beam at 280 KV and 40 ma for a total dose of 8Mrad.

EXAMPLE XIX

The procedures of Example XVIII are repeated with the difference thatthe top coat is replaced successively by those specified in ExamplesXXV - XXVII which follow with essentially equivalent results.

EXAMPLE XX

An electron polymerizable coating is formulated in the manner set forthin Example IX using the following materials:

    ______________________________________                                                             Parts by Weight                                          ______________________________________                                        (1) Polymer from Step 1, Example IX                                                                  30                                                     (2) Trimethylolpropane triacrylate                                                                   20                                                     (3) 2-ethylhexyl acrylate                                                                            50                                                     (4) 2-acryloyloxyethylphosphate                                                                      .75                                                    ______________________________________                                    

The coating composition is sprayed on a plastic substrate bearing acoating of vapor deposited stainless steel and cured by electron beamirradiation. The resultant film exhibits excellent adhesion as well asgood solvent resistance and corrosion resistance.

EXAMPLE XXI

An electron polymerizable coating is formulated in the manner set forthin Example IX using the following materials:

    ______________________________________                                                             Parts by Weight                                          ______________________________________                                        (1) Polymer from Step 1, Example IX                                                                  30                                                     (2) Pentaerythritol tetraacrylate                                                                    20                                                     (3) 2-ethylhexyl acrylate                                                                            50                                                     (4) ethylmethacryloyloxyethyl phosphate                                                              .3                                                     ______________________________________                                    

The coating composition is sprayed on a glass substrate bearing acoating of vacuum deposited aluminum and cured by an electron beam. Theresultant film exhibits outstanding solvent and corrosion resistance.

EXAMPLE XXII

Commercially available resins of high molecular weight may be used in thpreparation of low solids content coatings. Film forming solutions areprepared from Elvacite 2009 and Elvacite 2041 as set forth hereinafter.Elvacite 2009 and Elvacite 2041 are marketed by E. I. Du Pont de Nemours& Co., Inc. Electrochemicals Department are are described as methylmethacrylate polymers of medium and very high molecular weight,respectively. The number average molecular weights of the resins usedfor the present work is 57,000 (Elvacite 2009) and 240,000 (Elvacite2041); the corresponding weight average molecular weights are 106,000and 540,000.

    ______________________________________                                                        Parts by Weight                                                               A        B                                                    ______________________________________                                        Elvacite 2009     21.5       --                                               Elvacite 2041     --         23                                               2-ethylhexyl acrylate                                                                           44         46                                               Neopentylglycol acrylate                                                                        34         31                                               Methacryloyloxyethyl phosphate                                                                  0.5        0.5                                              ______________________________________                                    

Formulation A is reduced to spray viscosity using a 40/40/20 mixture ofmethylethylketone, toluene, and ethyl acetate, while formulation B isreduced to spray viscosity with a 50/50 mixture of toluene andmethylethyl ketone. The coating formulations obtained are sprayed uponplastic substrates previously decorated by vacuum deposition ofaluminum, and are cured thereon. The composite coatings so obtaineddisplay exceptional mar resistance and corrosion resistance.

EXAMPLE XXIII

The procedure of Example I is repeated with the exception that 2.5 partsof 2-methacryloxyethyl phosphate are employed. The cured films adherewell when dry but develop an unacceptable bluish haze and soften uponexposure to water.

EXAMPLE XXIV

A plural coated article including a vacuum deposited metal layer isprepared as follows.

A. preparation and Application of Base Coat

                  Step 1                                                          ______________________________________                                        Preparation of Polymeric Intermediate                                                         Mole Percent                                                                           Mole Percent                                         ______________________________________                                        (1) Adipic Acid   24         28                                               (2) Maleic Anhydride                                                                             8         5.6                                              (3) Neopentyl glycol                                                                            38         31.1                                             (4) Hexamethylene diisocyanate                                                                  16         22.1                                             (5) 2-hydroxyethylacrylate                                                                      14         13.2                                             ______________________________________                                    

Components (1), (2), and (3) are charged to a reaction vessel equippedin the usual manner for polyester synthesis (i.e., so that water can beremoved during the course of the reaction) and heated gradually to 230°C. When an acid value of less than 16 is obtained (average reactant time16 hours), the mixture is cooled to 150° C. and 0.04 weight percenthydroqinone is added. The mixture is further cooled to below 100° C. andreduced to 70% solids with butyl acrylate.

Component (4) is added at room temperature and the mixture is heated at60°-70° C. until an isocyanate level of 5% is obtained.

Component (5) is added at 70° C. and the mixture heated at 80°-100° C.until the isocyanate is completely reacted. The mixture is reduced to60% solids with equal parts of 2-hydroxyethylacrylate and butylacrylate.

                  Step 2                                                          ______________________________________                                        Preparation of Coating Formulation                                                                 Parts by Weight                                          ______________________________________                                        (1) Resin solution from I                                                                            60                                                     (2) 2-hydroxyethylacrylate                                                                           10                                                     (3) Hydroxyethylacrylate                                                                             20                                                     (4) Methylmethacrylate 40                                                     ______________________________________                                    

The listed components are mixed in indicated proportions by weight,sprayed on a plastic substrate and cured with an electron beam in anitrogen atmosphere at 280 KV, 40 ma for a total dose of 10 Mrads.

B. application of Metal Layer

A layer of type 430 stainless steel is deposited on the base coat by aconventional vacuum deposition technique employing electron beam heatingof the evaporant.

C. preparation and Application of Top Coat

Step 1. Preparation of Resin

An electron polymerizable coating is prepared from the followingmaterials in the manner hereinafter set forth:

    ______________________________________                                                             Parts by Weight                                          ______________________________________                                        (1) Methyl methacrylate                                                                              300                                                    (2) t-butylperoctoate  1.5                                                    (3) Toluene            300                                                    (4) 10% t-butylperoctoate in toluene                                                                 10                                                     ______________________________________                                    

A mixture of items 1 and 2 is added dropwise over a 2 hour period to areaction flask (equipped with a condenser, thermometer, agitator, anddropping funnel) containing item 3 maintained at reflux. The mixture isrefluxed two to three additional hours; item 4 is charged to the flashat the end of the first hour. The polymer so obtained has a numberaverage molecular weight of about 14,400.

    ______________________________________                                                              Parts by Weight                                                               A     B                                                 ______________________________________                                        (1) Polymer from Step 1 27      50                                            (2) Neopentylglycol diacrylate                                                                        35      20                                            (3) 2-ethylhexyl acrylate                                                                             38      24                                            (4) Phosmor M*          .3      .3                                            ______________________________________                                         *Phosmor M is a product of Yushi Seihin K.K., a subsidiary of Nihon Oil &     Fat Co., Ltd. and is primarily 2-methacryloyloxyethyl phosphate.         

The film forming top coat so obtained is applied by flow coating on thesurface of the article bearing the vacuum deposited metal and cured byelectron beam irradiation at 280 KV, 40ma for a total dose of 10 Mrads.

The resultant vapor metallized article passes cross-hatch adhesion test,can withstand a minimum of 50 rubs with a cloth soaked in methyl ethylketone. Also, the plural coated article is unaffected by immersion inwater at 90° F. for 240 hours and 10 day immersion in a 5% aqueoussodium chloride solution.

EXAMPLE XXV

The procedures of Example XXIV are followed with the difference that:

1. The polymer solution of (C) Step 1 is prepared using:

    ______________________________________                                                              Parts by Weight                                         ______________________________________                                        (a) Methyl methacrylate 200                                                   (b) t-butylperoctoate    3                                                    (c) Toluene             300                                                   (d) 7% t-butylperoctoate in toluene                                                                    10                                                   ______________________________________                                    

(The polymer obtained has a number average molecular weight of about7,000); and

2. the coating of (C) Step 2 contains .3 parts ofdi(2-methacryloyloxyethyl) phosphate instead of Phosmor M. The resultantvapor metallized article passes cross-hatch adhesion tests and canwithstand a minimum of 50 rubs with a cloth soaked in methyl ethylketone. Also, the plural coated article is unaffected by immersion inwater at 90° F. for 240 hours and 10 day immersion in a 5% aqueoussodium chloride solution.

EXAMPLE XXVI

The procedure of Example XXIV is repeated except that:

1. the polymer of (C) Step 1 is prepared by using

    ______________________________________                                                              Parts by Weight                                         ______________________________________                                        (1) Methyl methacrylate 194                                                   (2) Acrylic acid         6                                                    (3) t-butylperoctoate    1                                                    (4) Toluol              300                                                   (5) 10% t-butylperoctoate in Toluol                                                                    10                                                   ______________________________________                                    

(The polymer obtained has a number average molecular weight of about14,000); and (2) 0.6 parts of 2-acryloyloxyethyl phosphate are used asthe phosphate additive in (C) Step 2. The resultant vapor metallizedarticle passes cross-hatch adhesion tests, can withstand a minimum of 50rubs with a cloth soaked in methyl ketone, is unaffected by immersion inwater at 90° F. for 240 hours and is unaffected by 10 days immersion ina 5% aqueous sodium chloride solution.

EXAMPLE XXVII

The procedure of Example XXIV is repeated except that in (B) a layer ofaluminum is deposited by employing a tungsten filament to heat theevaporant; and the polymer of (C) Step 1 is prepared by using:

    ______________________________________                                                              Parts by Weight                                         ______________________________________                                        (1) Methyl methacrylate 150                                                   (2) Butyl methacrylate   45                                                   (3) Acrylic acid         5                                                    (4) t-butyl peroctoate   1                                                    (5) Toluene             300                                                   (6) 10% t-butylperoctoate in toluol                                                                    10                                                   ______________________________________                                    

The polymer obtained has a number average molecular weight of about14,000. The resultant vacuum metallized article passes cross-hatchadhesion tests, can withstand a minimum of 50 rubs with a cloth soakedin methyl ethyl ketone, is unaffected by immersion in water at 90° F.for 240 hours and is unaffected by 10 days immersion in a 5% aqueoussodium chloride solution.

EXAMPLE XXVIII

The procedure of Example XXIV is repeated with two exceptions. First thebase coat composition is prepared from commercial electron beampolymerizable resins as follows:

    ______________________________________                                                              Parts by Weight                                                               A     B                                                 ______________________________________                                        (1) RD2107-30*          40      --                                            (2) RD2278-58*          --      60                                            (3) hydroxyethylacrylate                                                                              20      20                                            (4) methyl methacrylate 50      40                                            ______________________________________                                         *Both of these resins are unsaturated polyurethanes manufactured by           Hughson Chemical Company of Erie, Pennsylvania. (1) is supplied as a          solution of 80% polymer, 20% 2-ethylhexyl acrylate; and (2) is supplied a     a solution of 70% polymer, 15% methyl methacrylate, and 15% 2-ethylhexyl      acrylate.                                                                

Second, .7 parts of di(2-acryloyloxyethyl) phosphate are employed as theorganophosphate ester component. The coated article so obtained passescross-hatch adhesion tests and can withstand a minimum of 50 rubs with acloth soaked in methyl ethyl ketone. The surface does not soften orchange colar, and the underlying metal is similarly unaffected by 240hours exposure to water at 90° F. No failure is observed in 240 hoursimmersion in a 5% aqueous sodium cloride solution.

EXAMPLE XXIX

The procedure of Example XXIV is followed with the exception that thevapor deposited metal is aluminum and the top coat is prepared usingcommercially available resins as follows:

    ______________________________________                                                            Parts by Weight                                                               A   B     C     D   E                                     ______________________________________                                        Acryloid B48N (solid basis)                                                                         35    0     0   15  0                                   Acryloid A21LV (solid basis)                                                                         0    23    23   0  65                                  2-ethylhexyl acrylate 30    40    40  35   5                                  Neopentylglycol diacrylate                                                                          35    37    0    0   0                                  1,6-hexanediol diacrylate                                                                            0     0    37   0  30                                  trimethylolpropane triacrylate                                                                       0     0    0   50   0                                  2-methacryloyloxyethylphosphate                                                                      .1    .5    .8  .4  .3                                 ______________________________________                                    

Acryloid B48N and Acryloid A21LV are commercially available materials.Acryloid A21LV is marketed by Rohm & Haas Co. and is described as amethyl methacrylate polymer having a T_(g) =105° C.; it is supplied as a30% by weight solution in a mixture of toluene, methyl ethyl ketone, andbutanol (in proportion by weight 50:40:10) at a Brookfield viscosity of210-280 cps. at 25° C. The number average molecular weight is about13,000. Acryloid B48N is marketed by Rohm & Haas Co. and is described asa methyl methacrylate copolymer having a T_(g) =50° C; it is supplied asa 45% by weight solution in toluene at a Brookfield viscosity of 6000 to10,000 at 25° C. The number of average molecular weight is about 15,000.

All of the above coatings are reduced to spray viscosity using an inertsolvent mixture of toluene, methylethyl ketone, butylacetate andisoproponal and are spray coated on the vacuum metallized surfaces. Thecoating is then cured by electron beam to give a total radiation dose of9 Mrads (voltage 275 KV, current 40ma).

The resultant coated articles pass cross-hatch adhesion tests and canwithstand 50 rubs with a cloth soaked in methyl ethyl ketone. Thesurface coating does not soften or change color, and the underlyingmetal is similarly unaffected by 240 hours exposure to water at 90° F.No failure is observed in 240 hours immersion in a 15% aqueous chloridesolution.

EXAMPLE XXX

A plural coated article including a vacuum deposited metal layer isprepared as follows:

A. A commercially available base coat lacquer Red Spot SM 1817 sold byRed Spot Paint and Varnish Company and including a urealkyd type polymeris applied to a glass substrate and cured by heating for 90 minutes at170° F.

B. An aluminum layer is deposited on the base coat by a conventionalvacuum deposition technique.

C. A top coat formulation having the following composition is prepared:

    ______________________________________                                                              Parts by Weight                                         ______________________________________                                        (1) Acryloid A21LV (solid basis)                                                                      32                                                    (2) 2-ethylhexyl acrylate                                                                             38                                                    (3) neopentylglycol diacrylate                                                                        30                                                    (4) ethylmethacryloyloxyethyl phosphate                                                                .4                                                   ______________________________________                                    

The coating is reduced to spray viscosity using a 40:10:10 mixture ofbutyl acetate, toluene, methylethyl ketone and isopropanol, sprayed ontothe vacuum metallized substrate, and then cured by an electron beam at atotal dose of 9 Mrad.

The resultant vacuum metallized article exhibits a taped cross hatchrating for adhesion to aluminum of 9 (a rating of zero corresponding tocomplete catastrophic removal of a coating and 10 corresponding to noremoval). The coated article also can withstand a 30 to 50 rubs with acloth soaked in methyl ethyl ketone and is unaffected by either 240 hourimmersion in water at 90° F. or 10 day immersion in a 5% aqueous sodiumchloride solution.

EXAMPLE XXXI

The procedure of Example XXX is repeated except that: (1) the lacquerbase coat employed is a melamine-formaldehyde resin; and (2) the topcoat formulaton is:

    ______________________________________                                                              Parts by Weight                                         ______________________________________                                        (1) Acryloid B48N (solid basis)                                                                       30                                                    (2) 2-ethylhexyl acrylate                                                                             37                                                    (3) neopentylglycol diacrylate                                                                        33                                                    (4) ethylacryloyloxyethyl phosphate                                                                    .6                                                   ______________________________________                                    

The resultant vacuum metallized article exhibits a taped cross-hatchrating for adhesion to aluminum of 8. The article can withstand 30 to 50rubs with a cloth soaked in methyl ethyl ketone and is unaffected byeither 240 hour immersion in water at 90° F or 10 day immersion in a 5%aqueous sodium chloride solution.

EXAMPLE XXXII

A plural coated article including a vacuum deposited metal layer isprepared as follows:

A. A base coat having the following formulation is prepared:

    ______________________________________                                                              Parts by Weight                                         ______________________________________                                        (1) Elvacite 6011* (40% solids in a                                            30/70 mixture of acetone and toluene)                                                                40.0                                                  (2) trimethylolpropane triacrylate                                                                    24.0                                                  (3) hydroxypropylacrylate                                                                              8.0                                                  (4) 2-ethylhexylacrylate                                                                              16.0                                                  (5) methyl ethyl ketone 12.0                                                  ______________________________________                                         *Elvacite 6011 is a methylmethacrylate polymer manufactured by Dupont. Th     inherent viscosity of a solution of .25 grams polymer in 50 ml chloroform     measured at 25° C in a No. 50 Cannon-Fenske Viscometer is .34.    

The above materials are mixed and the formulation reduced to sprayviscosity (No. 1 Zahn Cup, 40 secs) with a 1:1 mixture of toluene andbutyl acetate. The formulation is then sprayed on a plastic substrateand cured by exposure to electron beam irradiation as in previousexamples.

B. An antimony layer is deposited on the base coat by conventionalvacuum deposition technique using a tungsten filament to heat theevaporant.

C. A top coat is prepared from the following materials:

    ______________________________________                                                              Parts by Weight                                         ______________________________________                                        (1) Acryloid A21LV (30% non solids)                                                                   50.0                                                  (2) 1,6 hexane diol diacrylate                                                                        24.0                                                  (3) 2-ethylhexyl acrylate                                                                             26.0                                                  (4) Phosmor M            0.2                                                  ______________________________________                                    

These materials are mixed, reduced to spray viscosity with 1:1 tolueneand butyl acetate, sprayed on the vacuum metallized surface and cured byelectron beam irradiation (9 Mrad dose).

The plural coated article passes cross-hatch tape adhesion tests, andresists in excess of 50 rubs with a cloth soaked in methyl ethyl ketone.Also, the coated article resists exposure to water at 90° F. and 5%aqueous solution of sodium chloride for 240 hours.

EXAMPLE XXXIII

A plural coated article including a vacuum deposited metal layer isprepared as follows:

A. A base coat having the following formulation is prepared:

    ______________________________________                                                              Parts by Weight                                         ______________________________________                                        (1) Elvacite 6012*      40.0                                                  (2) trimethylolpropane triacrylate                                                                    24.0                                                  (3) hydroxypropylacrylate                                                                              8.0                                                  (4) 2-ethylhexylacrylate                                                                              16.0                                                  (5) methyl ethyl ketone 12.0                                                  ______________________________________                                         *Elvacite 6012 is a methylmethacrylate polymer manufactured by Dupont. Th     inherent viscosity of a solution of .25 grams polymer is 50 ml chloroform     measured at 25° C in a No. 5 Cannon-Fenske viscometer is .38.     

The above materials are mixed and reduced to spray viscosity (No. 1 ZahnCup, 40 Secs.) with a 1:1 mixture of toluene and butyl acetate. Theformulation is sprayed on a steel substrate and cured by exposure toelectron beam irradiation (9 Mrad dose) as in previous examples.

B. An aluminum layer is deposited on the base coat by conventionalvacuum deposition.

C. A top coat is prepared in accordance with the following:

1. A polymer is prepared as follows:

    ______________________________________                                                              Parts by Weight                                         ______________________________________                                        (1) Methyl methacrylate 300                                                   (2) t-butylperoctoate    1.5                                                  (3) Toluene             300                                                   (4) 10% t-butylperoctoate in toluene                                                                   10                                                   ______________________________________                                    

A mixture of items 1 and 2 is added dropwise over a 2 hour period to areaction flask (equipped with a condenser, thermometer, agitator anddropping funnel) containing item 3 maintained at reflux. The mixture isrefluxed two to three additional hours; item 4 is charged to the flaskat the end of the first hour. The polymer so obtained has a numberaverage molecular weight of about 13,000.

2. 50 parts by weight of the polymer prepared in (1) is combined with24.0 parts of hexanediol diacrylate, 26.0 parts of 2-ethyl hexylacrylate; and 0.2 parts of 2-methacryloylethyloxy phosphate.

These materials are mixed, reduced to spray viscosity with 1:1 tolueneand butyl acetate, sprayed on the vacuum metallized surface and cured byelectron beam irradiation as in previous examples.

The plural coated article passes cross-hatch tape adhesion tests, andresists in excess 50 rubs with a cloth soaked in methyl ethyl ketone.The article is also not adversely affected by exposure to water at 90°F. and a 5% aqueous solution of sodium chloride for 240 hours.

EXAMPLE XXXIV

A plural coated article including a vacuum deposited metal layer isprepared as follows:

A. The same base coat as employed in Example XXXIII is flow coated on aplastic substrate and cured by electron beam irradiation.

B. An antimony layer is deposited on the base coat by conventionalvacuum deposition.

C. A top coat is prepared in accordance with the following:

1. a polymer is prepared as follows:

    ______________________________________                                                              Parts by Weight                                         ______________________________________                                        (1) Methyl methacrylate 200                                                   (2) t-butylperoctoate    3.0                                                  (3) Toluene             300                                                   (4) 10% t-butylperoctoate in toluene                                                                   10                                                   ______________________________________                                    

A mixture of items 1 and 2 is added dropwise over a 2 hour period to areaction flask (equipped with a condenser thermometer, agitator, anddropping funnel) containing item 3 maintained at reflux. The mixture isrefluxed 2 to 3 additional hours; item 4 is charged to the flask at theend of the first hour. The polymer so obtained has a number averagemolecular weight of about 7,800.

2. 50 parts by weight of the polymer prepared in (1) is combined with24.0 of 1,6 hexane dioldiacrylate, 26.0 parts of 2-ethylhexyl acrylateand 0.2 parts of Phosmor M.

These materials are mixed, reduced to spray viscosity with 1:1 tolueneand butyl acetate, spray on the metallized surface and cured by electronbeam irradiation.

The plural coated article passes cross-hatch adhesion tests, and resistsin excess of 60 rubs with a cloth soaked in methyl ethyl ketone.Exposure for 10 days to either water at 90° F or 5% aqueous salt sprayproduces no deterious effects on the composite.

EXAMPLE XXXV

A plural coated article including a vacuum deposited metal layer isprepared as follows:

A. A base coat having a following formulation is prepared:

    ______________________________________                                                              Parts by Weight                                         ______________________________________                                        (1) Acryloid B-44 (40%)*                                                                              38.5                                                  (2) Trimethyolpropanetriacrylate                                                                      38.5                                                  (3) Hydroxypropylacrylate                                                                              7.7                                                  (4) 2 ethyl hexyl acrylate                                                                            15.3                                                  ______________________________________                                         *Acryloid B-44 is a methyl methacrylate copolymer having a T.sub.g of         60° C and has a Brookfield viscosity at 25° C of 855 to         1700. It is supplied as a 40% solution in a 95/5 toluene/methyl cellosolv     mix by Rohm & Haas Co.                                                   

The above materials are mixed and reduced to spray viscosity (No. 1 ZahnCup, 40 Secs.) with a 1:1 mixture of toluene and butyl acetate.

The formulation is applied to a glass substrate and cured by exposure toelectron beam irradiation (9 Mrad dose) as in previous examples.

B. An aluminum layer is deposited on the base coat by conventionalvacuum deposition.

C. The same top coat as employed in Example XXXIII, except for the useof 0.4 parts of ethylmethacryloyloxyethyl phosphate as theorganophosphate additive, is sprayed on the vacuum deposited metal andcured by electron beam irradiation.

The plural coated article passes the cross-hatch adhesion test as wellas the water and aqueous salt solution exposure tests at 240 hours andresists over 50 rubs with a cloth soaked in methyl ethyl ketone.

EXAMPLE XXXVI

A plural coated article including a vacuum deposited metal layer isprepared as follows:

A. A base coat having the following formulation is prepared:

    ______________________________________                                                              Parts by Weight                                         (1) Acryloid B-44       57.0                                                  (2) trimethylolpropane triacrylate                                                                    14.3                                                  (3) neopentylglycoldiacrylate                                                                          9.5                                                  (4) 2-ethylhexyl acrylate                                                                             19.2                                                  ______________________________________                                    

The above materials are mixed and the formulation reduced to sprayviscosity (No. 1 Zahn Cup, 40 secs.) with a mixture of 1:1 toluene andbutyl acetate. The formulation is then sprayed on a plastic substrateand cured by electron beam irradiation (9 Mrad dose).

B. An aluminum layer is deposited on the base coat by conventionalvacuum deposition technique.

C. A top coat, which is the same as that applied in Example XXXII exceptthat 0.3 parts of ethylmethacryloyloxyethyl phosphate are substitutedfor the Phosmor M, is sprayed on the vacuum metallized surface and curedby electron beam irradiation (9 Mrad dose).

The plural coated article passes the cross-hatch adhesion test as wellas the water and aqueous salt solution exposure test at 240 hours andresists in excess of 50 rubs with a cloth exposure in methyl ethylketone.

EXAMPLE XXXVII

A plural coated article including a vacuum deposited metal layer isprepared as follows:

A. a base coat having the same formulation as that of Example XXXVI issprayed on a plastic substrate.

B. an antimony layer is deposited on the base coat by conventionalvacuum deposition.

C. A top coat having the same formulation as that used in Example XXXIVexcept that 0.6 parts of methyl (2-methacryloyloxyethyl) phosphate issubstituted for the Phosmore M is sprayed on the vacuum metallizedsurface and cured by electron beam irradiation (9 Mrad dose).

The resultant article withstands a minimum of 50 rubs with a methylethyl ketone soaked cloth as well as 240 hours exposure to water at 90°F. and 5% aqueous salt solution and also passes to cross-hatch tapeadhesion test.

EXAMPLE XXXVIII

The procedure of Example XXXII are repeated except that 0.2 parts ofPhosmor M are included in the base coat formulation. The plual coatedarticles are comparable to those of Example XXXII.

EXAMPLE XXXIX

The procedure of Example XXXIII is repeated with the exception that 0.4parts of di(2-methacryloyloxyethyl) phosphate are included in the basecoat formulation. The plural coated articles are comparable to those ofExample XXXIII.

EXAMPLE XXXX

The procedure of Example XXXIV is repeated with the exception that 0.3parts of (2-methacryloyloxyethyl) phosphate are included in the basecoat. The plural coated articles are comparable to those of ExampleXXXIV.

EXAMPLE XXXXI

The procedure of Example XXXV is repeated with the exception that 0.6parts of di(2-acryloyloxyethyl) phosphate are included in the base coatformulation. The plural coated articles are comparable to those ofExample XXXV.

EXAMPLE XXXXII

The procedure of Example XXXVI is repeated with the exception that 0.8parts of methyl acryloyloxyethyl phosphate are included in the base coatformulation. The plural coated articles are of comparable quality withthose of Example XXXVI.

EXAMPLE XXXXIII

The procedure of Example XXXVII is repeated with the exception that 0.5parts of ethyl acryloyloxyethyl phosphate are included in the base coat.The plural coated articles are comparable to those of Example XXXVII.

EXAMPLE XXXXIV

The procedures of Example X are followed with the difference that thecoating formulation comprises 50 parts by weight polymer; 15 parts byweight neopentylglycol diacrylate; 10 parts by weightpentaerythritoltriacrylate; and 25 parts by weight of2-ethylhexylacrylate.

EXAMPLE XXXXV

A plural coated article is prepared according to the procedures ofExample XXXI with the difference that: the metal layer is deposited bysputtering an 80/20 chromium/iron alloy, and that the top coatformulation comprises 50 parts by weight polymer; 25 parts by weight2-ethylhexylacrylate; 25 parts neopentylglycoldiacrylate; and 0.4 partsethylmethacryloyloxyethyl phosphate.

It will be understood by those skilled in the art that modifications canbe made in the foregoing example and within the scope of the inventionas hereinbefore described and hereafter claimed.

We claim:
 1. An article of manufacture comprising a substrate and anadherent coating of radiation polymerized paint on the surface thereof,said paint, on a non-polymerizable solvent, pigment, initiator andparticulate filler-free basis, consisting essentially of the in situformed polymerization product of a film-forming solution of: (1) betweenabout 90 and about 10 parts of a thermoplastic vinyl polymer free ofolefinic unsaturation, having a number average molecular weight rangingfrom about 2,000 to about 250,000 and being prepared from at least about85 weight percent of monofunctional vinyl monomers; (2) between about 10and about 90 parts of vinyl monomer solvent for said polymer, up to 90weight percent of said solvent being selected from the group consistingof divinyl monomers, trivinyl monomers, tetravinyl monomers and mixturesthereof; and (3) between and about 0.05 and about 1.0 parts per 100parts of the total of said thermoplastic vinyl polymer and said vinylsolvent monomers of a mono- or diester of phosphoric acid bearing one ormore sites of vinyl unsaturation and having the formula: ##STR6## where:R = H, Cl, CH₃ A = c_(n) H_(2n), 2≦n ≦6 R' = h, c₁ to C₄ alkyl or C₁ toC₄ chloro- or bromoalkyl.
 2. An article in accordance with claim 1,wherein the surface to which the radiation polymerized paint is adheredcomprises a vapor deposited metal layer.
 3. An article in accordancewith claim 2 wherein said vapor deposited metal is stainless steel. 4.An article in accordance with claim 2 wherein said vapor deposited metalis aluminum.
 5. An article in accordance with claim 2 wherein said basecoat film is the in situ formed polymerization product of a solutionwhich, exclusive of non-polymerizable solvent, pigments and particulatefillers, consists essentially of (1) between about 90 and about 10 partsof a thermoplastic vinyl polymer free of olefinic unsaturation andprepared from at least about 85 weight percent of monofunctional vinylmonomers and (2) between about 10 and about 90 parts of vinyl solventmonomers for said vinyl polymer, at least about 10 weight percent ofsaid solvent monomers being selected from the group consisting ofdivinyl monomers, trivinyl monomers, tetravinyl monomers and mixturesthereof.
 6. A process for making an abrasion and corrosion resistantplural coated article comprising:A. coating a surface of a substratewith a base coat composition; B. curing the base coat composition toform a film; C. vapor depositing a layer of metal on the surface of saidbase coat composition film; D. coating the metal bearing surface with atop coat composition which, exclusive of non-polymerizable solvents,pigments, initiators and particulate fillers, consists essentially of:(1) between about 90 and about 10 parts of a thermoplastic vinyl polymerfree of olefinic unsaturation and prepared from at least about 85 weightpercent of monofunctional vinyl monomers; (2) between about 10 and about90 parts of vinyl solvent monomers for said vinyl polymer, at leastabout 10 weight percent of said solvent monomers being selected from thegroup consisting of divinyl monomers, trivinyl monomers, tetravinylmonomers and mixtures thereof; and (3) between about 0.05 and about 1.0parts per 100 parts of the total of said thermoplastic vinyl polymer andsaid vinyl solvent monomers of a mono- or diester of phosphoric acidbearing one or more sites of vinyl unsaturation and having the formula:##STR7## where: R = H, C1 or CH₃ A = c_(n) H_(2n), 2≦n≦ 6 R' = h, c₁ toC₄ chloro- or bromoalkyl or C₁ to C₄ alkyland E. curing the top coatcomposition to form a film by exposure to radiation.
 7. A process inaccordance with claim 6 wherein said top coat composition is cured byexposure to ionizing radiation.
 8. A process in accordance with claim 6wherein said top coat composition contains a photoinitiator and is curedby exposure to ultraviolet light.
 9. A process in accordance with claim6 wherein said base coat composition is a lacquer comprising a curableor fusible resin in a volatile solvent.
 10. A process in accordance withclaim 6 wherein said base coat composition, exclusive ofnon-polymerizable solvents, pigments, initiators and other non-reactivecomponents, consists essentially of (1) between about 90 and about 10parts of a thermoplastic vinyl polymer free of olefinic unsaturation andprepared from at least about 85 weight percent of monofunctional vinylmonomers and (2) between about 10 and about 90 parts of vinyl solventmonomers for said vinyl polymer, at least about 10 weight percent ofsaid solvent monomers being selected from the group consisting ofdivinyl monomers, trivinyl monomers, tetravinyl monomers and mixturesthereof.
 11. A process in accordance with claim 6 wherein said base coatcomposition, exclusive of non-polymerizable solvents, pigments,initiators and other non-reactive components, consists essentially of(1) between about 90 and about 10 parts of a thermoplastic vinyl polymerfree of olefinic unsaturation and prepared from at least about 85percent of monofunctional vinyl monomer units; (2) between about 10 andabout 90 parts of vinyl solvent monomers for said vinyl polymer, atleast about 10 weight percent of said solvent monomers being selectedfrom the group consisting of divinyl monomers, trivinyl monomers,tetravinyl monomers and mixtures thereof; and (3) between about 0.05 andabout 1.0 parts per 100 parts of the total of said thermoplastic vinylpolymer and said vinyl solvent monomers of a mono- or diester ofphosphoric acid bearing one or more sites of vinyl unsaturation andhaving the formula: ##STR8## where: R = H, Cl or CH₃ A = c_(n) H_(2n),2≦n≦6 R' = h₁ c₁ to C₄ alkyl or C₁ to C₄ chloro- or bromo-alkyl.
 12. Aprocess in accordance with claim 6 wherein said base coat composition,exclusive of non-polymerizable solvents, pigments and other non-reactivecomponents, consists essentially of: (1) between about 90 and about 10parts of an alpha-beta olefinically unsaturated urethane modifiedorganic resin; and (2) between about 10 and about 90 parts of vinylsolvent monomers.
 13. A plural coated abrasion and corrosion resistantarticle comprising:A. a substrate; B. a base coat film on a surface ofsaid substrate; C. a layer of metal on the surface of said base coatfilm; and D. a top coat film on said metal layer, said top coat filmcomprising the in situ formed polymerization product of a solutionwhich, exclusive of non-polymerizable solvent, pigments and particulatefillers, consists essentially of: (1) between about 90 and about 10parts of thermoplastic vinyl polymer free of olefinic unsaturation andprepared from at least 85 weight percent of monofunctional vinylmonomers; (2) between about 10 and about 90 parts of vinyl solventmonomers for said vinyl polymer, at least about 10 weight percent ofsaid solvent monomers being selected from the group consisting ofdivinyl monomers, trivinyl monomers, tetravinyl monomers and mixturesthereof; and (3) between about 0.05 and about 1.0 parts per 100 parts ofthe total of said thermoplastic vinyl polymer and said vinyl solventmonomers of a mono- or diester of phosphoric acid bearing one or moresites of vinyl unsaturation and having the formula: ##STR9## A = C_(n)H_(2n), 2≦n≦6 R' = H, C₁ to C₄ alkyl or C₁ to C₄ chloro- or bromoalkyl.14. An article in accordance with claim 13 wherein said layer of metalis vapor deposited.
 15. An article in accordance with claim 13 whereinsaid base coat film is the in situ cured product of a lacquer comprisinga curable or fusible resin in a volatile solvent.
 16. An article inaccordance with claim 13 wherein said base coat film comprises the insitu formed polymerization product of a solution which, exclusive ofnon-polymerizable solvents, pigments and particulate fillers, consistsessentially of (1) between about 90 and about 10 parts of athermoplastic vinyl polymer free of olefinic unsaturation and preparedfrom at least about 85 weight percent of monofunctional vinyl monomerunits; (2) between about 10 and about 90 parts of vinyl solvent monomersfor said vinyl polymer, at least about 10 weight percent of said solventmonomers being selected from the group consisting of divinyl monomers,trivinyl monomers, tetravinyl monomers and mixtures thereof; and (3)between about 0.05 and about 1.0 parts per 100 parts of the total ofsaid thermoplastic polymer and said vinyl solvent monomers of a mono- ordiester of phosphoric acid bearing one or more sites of vinylunsaturation and having the formula: ##STR10## where: R = H, Cl or CH₃ A= c_(n) H_(2n), 2≦n≦ 6 R' = h, c₁ to C₄ alkyl or C₁ to C₄ chloro- orbromoalkyl.
 17. An article in accordance with claim 13 wherein said basecoat film comprises the in situ formed polymerization product of asolution which, exclusive of non-polymerizable solvents, pigments andother non-reactive components, consists essentially of (1) between about90 and about 10 parts of an alpha-beta olefinically unsaturated urethanemodified organic resin containing between about 0.5 and about 5 units ofolefinic unsaturation per 1,000 units of molecular weight; and (2)between about 10 and about 90 parts of vinyl solvent monomers.